A fine cobalt-toughened Al2O3-TiC ceramic and its wear resistance

Mechanical ball milling is the most common method for mixing ceramic powders with a ductile phase such as metal particles. In this paper, a new powder processing way is presented. Al2O3 and TiC powders are coated with a layer of metal cobalt using the chemical deposition process. The thickness of the metal cobalt film can be controlled by adjusting the deposition conditions. The Co-coated Al2O3 (Al2O3–Co) and TiC (Tic–Co) powders are mixed at the rate of 7:3 and hot-press sintered into a fine Al2O3–TiC–Co (ATC) ceramic. The main properties, erosion behaviour, abrasion behaviour, wear mechanism and wear resistance of Al2O3-TiC-Co and Al2O3–30 wt% TiC (AT30) ceramics are determined by transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, etc. It is shown that the ATC ceramic possesses improved mechanical properties. Because of the existence of metal cobalt in the grain boundaries, the bonding strength between grains is increased, and this prevents spalling of grains during wear. Experimentation indicates that ATC is more resistant to wear than Al2O3–TiC ceramic. The relationship between their mechanical properties and wear resistance is also discussed in this paper.     

Transient thermal stress analysis of an edge crack in a functionally graded material

An edge crack in a strip of a functionally graded material (FGM) is studied under transient thermal loading conditions. The FGM is assumed having constant Young's modulus and Poisson's ratio, but the thermal properties of the material vary along the thickness direction of the strip. Thus the material is elastically homogeneous but thermally nonhomogeneous. This kind of FGMs include some ceramic/ceramic FGMs such as TiC/SiC, MoSi₂/Al₂O₃ and MoSi₂/SiC, and also some ceramic/metal FGMs such as zirconia/nickel and zirconia/steel. A multi-layered material model is used to solve the temperature field. By using the Laplace transform and an asymptotic analysis, an analytical first order temperature solution for short times is obtained. Thermal stress intensity factors (TSIFs) are calculated for a TiC/SiC FGM with various volume fraction profiles of the constituent materials. It is found that the TSIF could be reduced if the thermally shocked cracked edge of the FGM strip is pure TiC, whereas the TSIF is increased if the thermally shocked edge is pure SiC.     

Diffusion couple preparation using cast coating technique

A novel diffusion couple preparation technique suitable for the measurement of diffusivities in molten metals and semiconductors via the long capillary method has been developed. The so-called cast coating technique involves casting of a molten alloy, which contains the impurity element to be diffused, on top of the pure solvent rods. Planar, oxide and defect free interfaces were produced at the alloy/solvent junction of the diffusion couple following basic solidification principles and a controlled atmosphere. It was noted that the thermal properties of both the molten alloy and the mould were critical in determining the location and planarity of the diffusion couple interface. The Sn/Sn-1 wt% Au and Pb/Pb-1 wt% Au diffusion couples in conjunction with moulds machined from graphite, porous graphite and a machinable ceramic were chosen as a case study.     

On the mechanical behavior of a functionally graded micro-beam subjected to a thermal moment and nonlinear electrostatic pressure

In the present work, mechanical behavior of a functionally graded cantilever micro-beam subjected to a nonlinear electrostatic pressure and temperature changes has been studied. It has been assumed that the top surface is made of pure metal and the bottom surface from a metal–ceramic mixture. The ceramic constituent percent of the bottom surface varies from 0% to 100%. In addition to the Volume Fractional Rule of material, exponential function has been used for representation of continuous gradation of the material properties through micro-beam thickness. Attention being paid to the ceramic constituent percent of the bottom surface, five different types of FGM micro-beams have been investigated. Nonlinear integro-differential thermo-electro mechanical equation based on Euler–Bernoulli beam theory has been derived and solved using Step-by-Step Linearization Method and Finite Difference Method. The effects of temperature changes and the electrostatic pressure on the deflection and stability of FGM micro-beams having various amounts of the ceramic constituent have been studied and normal stress distributions in the cross section along the beam thickness have been given and compared with a classic metal beam.     

Influence of the particle size and phase type of zirconia on the fabrication and residual stress of zirconia/stainless-steel 304 functionally gradient material

Tetragonal zirconia polycrystal (TZP)/stainless steel 304 (SUS304)- and ZT [50 vol % monoclinic zirconia polycrystal (MZP) + 50 vol % TZP]/SUS304-functionally gradient material (FGM) were fabricated by pressureless sintering, and the sintering properties and residual stresses of this proposed FGM were compared with directly jointed material. The defects in the sintered specimens, such as warping, frustum formation, delamination, and cracking, which originated from the different shrinkage and sintering behavior of ceramic and metal, could be controlled by the adjustments in terms of the particle size and phase type of zirconia. The residual stresses induced on the ceramic and metal regions of FGM were characterized by the X-ray diffraction method, which were relaxed as the thickness and number of compositional gradient layers were increased. The residual stresses in TZP/SUS304-FGM show irregular patterns resulting from sintering defects and thermal expansion mismatch. In ZT/SUS304-FGM, compressive stress is induced on the ceramic regions by the volume expansion of MZP that resulted from the t m ZrO₂ phase transformation on cooling. Also, compressive stress is induced on the metal regions by the constraint of warping and frustum formation that must be created to the metal direction caused by the difference of the coefficient of thermal expansions. As a consequence, it has been verified that the residual stresses generated on FGM are dominantly influenced by the thickness and number of compositional gradient layers, and the sintering defects and residual stresses can be controlled by the decrease of the difference of the shrinkage and sintering behavior of each component.     

陶瓷增强铝合金互渗相复合材料的半固态设计和成形

目的 开发一种针对金属-陶瓷互渗相复合材料生产的高效方法,以提升该类材料在高温高负荷环境中的使用寿命和工作可靠性。方法 采用数值扫描技术研究了半固态成形过程,以铝合金为金属成分、氧化铝开孔体为陶瓷成分,制备了复合材料。通过模拟2种腔体（开放式和封闭式）的金属陶瓷压铸成形过程模拟不同的模腔设计,详细分析了腔体内的压力水平及其分布情况,探讨了压铸温度、金属液相体积分数等参数对材料成形质量的影响。结果 封闭模腔能够在成形过程中产生更加均匀的压力分布,有助于减少如气孔、未渗透区域等材料缺陷,并提高金属与陶瓷之间的互渗质量。与封闭模腔相比,开放模腔在控制材料均匀流动和确保渗透效果方面效果较差。结论 采用封闭模腔的半固态成形工艺能显著提升金属-陶瓷互渗相复合材料的整体质量和性能,有效减少成形缺陷,为高性能金属-陶瓷复合材料的制备提供了一种有效路径。     

Diffusion bonding of a nickel (chromium) alloy to zirconia: Mechanical properties and interface microstructures

Diffusion bonding of a Ni(Cr) alloy with ZrO₂ has been studied. It was found that the processes were controlled by chemical reactions at the metal/ceramic interface forming compounds within the composition range NiO_1–x Cr₂O_3–y ZrO_2–z (0<x,y,z<1). Reaction products were characterized by examination of the fractured metal/ceramic halves and from cross-sections using optical, scanning and transmission electron microscopy and energy dispersive X-ray microanalysis. These metallographic studies indicate that the interface reactions are accompanied by local melting indicating a possible eutectic reaction following interdiffusion. Pre-oxidizing the metal foil enhances these reactions and lowers the reaction temperatures. Differential thermal analysis found endotherms at 1050 and 1110 °C with sintered NiCr/ZrO₂ powders, and at 980 and 1100 °C when pre-oxidized powders were used. These are shown to be associated with local melting at the metal/ceramic interface. This thus explains the existence of a critical bonding temperature for good-quality diffusion bonding, where a minimum temperature has to be satisfied for the eutectic reaction to occur.     

功能梯度材料梁在后屈曲构型附近的自由振动

基于轴线可伸长杆的几何非线性理论,建立了由陶瓷和金属两种材料组成的功能梯度(FGM)梁在轴向载荷作用下后屈曲横向自由振动的精确模型,采用打靶法数值求解了一端可移简支一端固定的功能梯度梁在后屈曲附近的小振幅自由振动,获得了线性振动的响应,给出了不同梯度指标下FGM梁前三阶固有频率与载荷之间的特征关系曲线.数值结果表明,屈曲前各阶频率随轴向力的增加而降低,而屈曲后轴向力对各阶频率影响不同     

Studies of ceramic-liquid metal reaction interfaces

An investigation has been made of the nature and extent of chemical reactions between various liquid metals and a range of engineering-grade ceramics typically used as cutting tool inserts. Such possible reactions are relevant to chemical wear effects during metal cutting but also relate to liquid metal containment by ceramics and ceramic-metal joining. The experimental procedure has involved immersing pre-polished ceramic sections in liquid metals for controlled times with subsequent sectioning and examination of the reaction interface. The ceramics studied were two alumina-based materials and five silicon nitrides and sialons. The metals were pure iron, pure nickel and four iron-nickel alloys (a mild steel, a stainless steel and two nickel-based superalloys) and span a range of Fe-Ni compositions. The reaction rates of the alumina materials were found to be much lower than those of the silicon nitride-based materials and reflect the chemical stability of the Al-O bond array. Zirconia-toughened alumina showed little evidence of reaction with clean iron alloys but substantial attack by oxygen-containing iron-based materials was found resulting in the formation of iron-aluminium spinel reaction products. Al₂O₃-TiC/N exhibited preferential metal attack of the carbonitride phase with dissolution and/or replacement of the TiC/N dispersion. Within the silicon nitride-based group, ferrous alloys were found to be more damaging than mainly nickel alloys and silicon nitrides were more readily attacked than sialons. The difference in behaviour between the sialons and silicon nitrides is attributed to alumina additions in the former group of materials increasing resistance to attack by molten metals. A detailed mechanism of attack for these mixed-phase ceramics is proposed whereby a silicon concentration gradient is established from the crystalline ceramic phases, through the glassy binding phase, to the metal. The result is dissolution of the crystalline phase and an increase in volume fraction of the glassy binder at the metal-ceramic interface with concomitant progressive disruption of the ceramic microstructure.     

A model for interface cracks in layered orthotropic solids: Convergence of modal decomposition using the interaction integral method

The mode‐partitioning problem for bimaterial interfaces is still not resolved by the classical fracture mechanics approach in a satisfactory manner. Stress oscillations and overlapping crack faces are a direct consequence of the rigorous solution of the elastic boundary value problem, if the constitutive law changes discontinuously across the interface. Conversely, continuously varying material properties, also referred to as functionally graded materials (FGM), avoid these physically not admissible drawbacks. In this case the crack tip fields are of the same nature as those known from homogeneous materials. Therefore, the well‐established stress intensity factor concept can be used without any changes. Following this motivation an FGM‐interface model for delaminated composite beam structures was developed and its characteristics with respect to the modal decomposition of the crack tip fields were investigated. The considered beam structures consisted of two orthotropic layers, each of a different material. The spatial variation of the material properties in the interface region was modeled by a tanh ‐function introducing one transition parameter that controlled the FGM‐gradient. Four load cases were analyzed for each structural configuration: either a unit normal force or a unit bending moment was imposed on each end of the split beam. Thus, any load case can be simply reconstructed from the presented results by means of superposition. The stress intensity factors for modes I and II were then evaluated using an interaction integral method along with the finite element method. The corresponding results are given depending on the mesh density of the interface region, the integration domain and the transition parameter. In this manner, the influence of the transition parameter on the mode ratio and on the convergence behavior of the modal decomposition scheme with respect to its integration domain was identified. Finally, the ability of the FGM‐interface model to represent bimaterial interfaces while still maintaining the advantages of crack analysis in homogeneous materials was highlighted. Copyright © 2008 John Wiley & Sons, Ltd.     

The Application of Flame and Plasma Sprayed Coatings for Cast Iron Molds

Molds made of grey iron for casting iron are subjected to severe temperature fluctuations very similar to the die casting process except for the high pressure erosion that occurs due to molten metal. Therefore, the main life limiting damage for molds is the formation of surface cracks arising from thermal fatigue. Various flame and plasma sprayed coatings were investigated to extend the life of molds for casting iron. Coating materials studied include plasma sprayed ceramic coatings with bond coat (NiCrAl, NiCrAlY, and NiCrAlCoY) as well as powder flame sprayed oxidation resistant alloys (NiCr, NiAl, and NiCrAl). The results of simulated cyclic furnace tests from room temperature to 1100°C in air indicated that the failure occurred along the interface between the bond coat and the iron substrate due to iron oxidation rather than the interface between the ceramic coating and the bond coating for superalloy substrate. The results of field tests are also discussed.     

Effect of BaSO4 on the interfacial phenomena of high-alumina refractories with Al-alloy

The performance of high-alumina refractories used for aluminium casting significantly impacts the efficiency of metal production. The interfacial reactions with Al-alloys cause corundum and magnesium spinel deposition on the refractory surface, leading to refractory degradation. An experimental study was conducted to investigate the influence of varying barium sulphate (BaSO₄) concentrations in a high-alumina refractory on its interfacial reactions with molten Al-alloy in a horizontal tube furnace at 1523 K (1250 °C) under inert conditions. This study showed that the Al-alloy reactions with pure BaSO₄ would form barium aluminates at the interface. However, in the Al-alloy/refractory system, the interfacial behaviour was strongly influenced by the relative amount of BaSO₄, such that up to 5 wt%, the extent of alloy penetration into the refractory increased with increasing BaSO₄ contents. Electron-probe micro-analyser and X-ray diffraction studies indicated that the composition of the interface for these refractories was augmented with barium silicates and diminishing anorthite phases. In the presence of 10 wt% BaSO₄, the extent of metal penetration into the refractory decreased, whilst for 20% BaSO₄, the penetration was higher; these results were attributed to the interfacial presence of celsian (BaAl₂Si₂O₈) and unreacted barium sulphates, respectively. This study suggests that maximising the celsian formation at the interface is critical for optimising the BaSO₄ concentration for improving the refractory’s performance for Al-casting.     

Abrasive wear behavior of monolithic alloy,homogeneous and functionally graded aluminum (LM25/AlN and LM25/SiO2) composites

Functionally graded metal matrix composites (MMCs) and homogenous composites (Al/AlN and Al/SiO₂-10 wt%) have been fabricated through centrifugal casting and liquid metallurgy route, respectively. The properties of these composites were compared with aluminum alloy. Microstructural characteristics and hardness were studied on the surfaces of functionally graded materials (FGMs), homogenous composites, and unreinforced aluminum alloy using an optical microscope and a Vickers micro hardness tester, respectively. Tensile test was carried out on the outer and inner sections of FGMs and specimens from homogenous composites and alloy utilizing universal testing machines (UTMs). Three-body abrasive wear test was conducted for different loads and speeds to study their effect on the surfaces of composites and alloy using dry abrasion tester. Microstructural and hardness results reveal that the outer surface of aluminum nitride (AlN)-reinforced FGM has a particle-enriched region with the highest hardness. Tensile strength was found higher in both homogenous composites compared to zones of their FGMs. Abrasion wear rate was found increased with increase in load and decreased with increase in speed. The outer surface of AlN-reinforced FGM has higher wear resistance followed by the outer surface of SiO₂-reinforced FGM. Scanning Electron Microscopy (SEM) analysis was performed on worn-out surfaces and observed particle-enriched outer surface of Al/AlN FGM with less abrasion.     

Physical and electrical properties of polyimide/ceramic hybrid films prepared via non-hydrolytic sol–gel process

In this study, TiO₂ and SiO₂ were chosen as ceramic fillers in the 3,3′,4,4′-benzophenone tetracarboxylic dianhydride–4,4′-oxydianiline (BTDA–ODA) polyimide matrix. Physical properties of hybrids with up to 30 wt% SiO₂ and 7 wt% TiO₂ were evaluated and discussed. Nano-size ceramic particles were prepared by non-hydrolytic sol–gel (NHSG) process. SEM micrographs show that both films have nano-sized ceramic particles with a narrow size distribution. Thermal conductivities of the hybrids increase from 0.12 to 0.21 W/m-K, as the SiO₂ and TiO₂ in the hybrid increases from 0 to 30 and 7 wt%, respectively. Electrical surface resistivity slightly decreases with increasing ceramic filler content. Dielectric constant of the hybrid increases from 2.45 to 2.72 with the incorporation of the 7 wt% (5.4 vol%) TiO₂. Water absorption decreases considerably with increasing filler content. With 30 wt% (20.2 vol%) SiO₂ addition, the water absorption of the hybrid film reduces by 85% from that of pure polyimide.     

Laser metal deposition of functionally graded Ti6Al4V/TiC

Functionally graded materials (FGMs) are advanced materials with improved properties that enable them to withstand severe working environment which the traditional composite materials cannot withstand. FGM found their applications in several areas which include: military, medicine and aerospace. Various manufacturing processes are used to produce functionally graded materials that include: powder metallurgy, physical vapour deposition, chemical vapour deposition process and laser metal deposition process. Laser metal deposition (LMD) process is an additive manufacturing process that can be used to produce functionally graded material directly from the three dimensional (3D) computer aided design (CAD) model of the part in one single process. LMD process is a fairly new manufacturing process and a highly non-linear process. The process parameters are of great importance in LMD process and they need to be optimized for the required application. In this study, functionally graded titanium alloy composite was produced using optimized process parameters for each material combination as obtained through a model that was developed in an initial study and the FGM was characterized through metallurgical, mechanical and tribological studies. The results show that the produced FGM has improved properties when compared to those produced at constant processing parameters for all material combinations.     

Response of spray-deposited,stirred-cast and conventional cast Pb-Sn alloys to deformation in the semi-solid state

Pb-35 wt% Sn alloys were deformed in the semi-solid state. The effects of the initial microstructures, deformation temperatures and deformation rates on the microstructures and the formability of the alloy were studied. A physical phenomenological model is proposed to explain the different behaviours of the stress-strain curves of semi-solid forming of various materials under various conditions. Three different processes, spray deposition (S/D), semi-solid synthesizing (SSS) and conventional casting (CC) were used to produce the Pb-35 wt% Sn alloys with different initial microstructures. Two strain rates, (0.083 and 0.00083 s^–1) and two deformation temperatures, (190 and 200°C) were used in this study. There is no significant variation in particle size and in sphericity during semi-solid forming of Pb-35wt% Sn alloys. The deformation stress increases monotonically as strain increases during semi-solid deformation of S/D materials, which consist of smaller solid particles. However, for SSS and CC materials, which consist of larger solid particles, the deformation stress increases in the beginning to a local maximum, then decreases to a minimum before it starts to increase again as strain increases. This phenomenon is more noticeable at lower deformation temperatures and higher strain rates. The deformation stresses required for deformation at higher deformation rates and at lower deformation temperatures are larger than those at lower deformation rates and at higher deformation temperatures, respectively.     

Preparation of AlN-Cu composite powders by electroless plating of controlled oxidized nitride particles to prevent degradation by hydrolysis

The present work describes the preparation of AlN-Cu composite powders by electroless plating. Initially, the hydrolysis reaction of the ceramic particles in the electroless solution was studied as a reference element for the design of a protective surface barrier that enabled the coating process, with no ceramic phase degradation. The metal source of the electrolytic bath was copper sulfate, with formaldehyde as the reducing agent, under alkaline conditions of pH 12. The microstructural characterization indicated the formation and growth of aluminum hydroxides from AlN particles, inhibiting the coating of Cu by increasing the OH⁻ ions in the solution. As the exposure time increased, the ellipsoidal bayerite grew from AlN and transformed into prismatic particles of the thermodynamically more stable gibbsite phase. To prevent the degradation of AlN, a controlled oxidation stage was implemented to form a protective barrier of non-reactive alumina on the surface through thermal treatment in oxidizing atmospheres. An atmosphere of dry air was found to be more appropriate than pure oxygen for the formation of a continuous and dense layer of crack-free alumina on nitride surfaces, and a temperature of 1000 °C for 1 h enabled the formation of 3.9 by weight of α-Al₂O₃, capable of reducing the hydrolysis reaction of AlN. The process of autocatalytic deposition on the passivated particles, applied in three consecutive steps of metallization, led to AlN-Cu composite powders with 29 wt% Cu. Finally, the coated powders were treated in a hydrogen-reducing atmosphere at 400 °C to remove traces of the Al(OH)₃ phase encountered, as well as to improve the adhesion of the nanostructured deposit of the cauliflower-like structure to the AlN surfaces, obtaining AlN-Cu composite powders suitable for the preparation of metal/ceramic composites.     

Acid aluminum phosphate for the binding and coating of materials

This is a review of acid aluminum phosphate for the binding and coating of materials. The acid aluminum phosphate in the form of a solution obtained by dissolving aluminum hydroxide in phosphoric acid, with a P/Al molar ratio of 23, is effective for the binding of fibrous or particulate materials. Porous ceramic articles are made using this binder by wet forming, followed by heat treatment. The binder resides at the junction of the adjacent fibers in the porous fibrous ceramic article. No free binder was observed in fibrous or particulate articles. The porosity is 45%–90% in fibrous articles, and is 25%–82% in particulate articles. Porosity above 61% in particulate articles is attained by adding carbon particles and subsequent removal of them by combustion. The binder proportion is 3–10 wt% in fibrous articles, and is 0.1 wt% in particulate articles. Porous ceramic articles made using a silica binder instead of the acid aluminum phosphate binder are inferior in permeability, mechanical properties and creep resistance, and exhibit a wider pore size distribution. Free silica binder was observed in articles made with the silica binder. The acid aluminum phosphate with a P/Al ratio of 12 or 23 is also effective for coating materials, particularly graphite for the purpose of oxidation protection.     

Cohesive fracture modeling of elastic-plastic crack growth in functionally graded materials

This work investigates elastic-plastic crack growth in ceramic/metal functionally graded materials (FGMs). The study employs a phenomenological, cohesive zone model proposed by the authors and simulates crack growth by the gradual degradation of cohesive surfaces ahead of the crack front. The cohesive zone model uses six material-dependent parameters (the cohesive energy densities and the peak cohesive tractions of the ceramic and metal phases, respectively, and two cohesive gradation parameters) to describe the constitutive response of the material in the cohesive zone. A volume fraction based, elastic-plastic model (extension of the original Tamura-Tomota-Ozawa model) describes the elastic-plastic response of the bulk background material. The numerical analyses are performed using WARP3D, a fracture mechanics research finite element code, which incorporates solid elements with graded elastic and plastic properties and interface-cohesive elements coupled with the functionally graded cohesive zone model. Numerical values of volume fractions for the constituents specified at nodes of the finite element model set the spatial gradation of material properties with isoparametric interpolations inside interface elements and background solid elements to define pointwise material property values. The paper describes applications of the cohesive zone model and the computational scheme to analyze crack growth in a single-edge notch bend, SE(B), specimen made of a TiB/Ti FGM. Cohesive parameters are calibrated using the experimentally measured load versus average crack extension (across the thickness) responses of both Ti metal and TiB/Ti FGM SE(B) specimens. The numerical results show that with the calibrated cohesive gradation parameters for the TiB/Ti system, the load to cause crack extension in the FGM is much smaller than that for the metal. However, the crack initiation load for the TiB/Ti FGM with reduced cohesive gradation parameters (which may be achieved under different manufacturing conditions) could compare to that for the metal. Crack growth responses vary strongly with values of the exponent describing the volume fraction profile for the metal. The investigation also shows significant crack tunneling in the Ti metal SE(B) specimen. For the TiB/Ti FGM system, however, crack tunneling is pronounced only for a metal-rich specimen with relatively smaller cohesive gradation parameter for the metal.     

Stochastic Finite element analysis of the free vibration of functionally graded material plates

The superior properties of functionally graded materials (FGM) are usually accompanied by randomness in their properties due to difficulties in tailoring the gradients during manufacturing processes. Using the stochastic finite element method (SFEM) proved to be a powerful tool in studying the sensitivity of the static response of FGM plates to uncertainties in their material properties. This tool is yet to be used in studying free vibration of FGM plates. The aim of this work is to use both a First Order Reliability Method (FORM) and the Second Order Reliability Method (SORM), combined with a nine-noded isoparametric Lagrangian element based on the third order shear deformation theory to investigate sensitivity of the fundamental frequency of FGM plates to material uncertainties. These include the effect of uncertainties on both the metal and ceramic constituents. The basic random variables include ceramic and metal Young’s modulus and Poisson’s ratio, their densities and ceramic volume fraction. The developed code utilizes MATLAB capabilities to derive the derivatives of the stiffness and mass matrices symbolically with a considerable reduction in calculation time. Calculating the eigenvectors at the mean values of the variables proves to be a reasonable simplification which significantly increases solution speed. The stochastic finite element code is validated using available data in the literature, in addition to comparisons with results of the well-established Monte Carlo simulation technique with importance sampling. Results show that SORM is an excellent rapid tool in the stochastic analysis of free vibration of FGM plates, when compared to the slower Monte Carlo simulation techniques.